Manufacture of synthetic resins from unsaturated hydrocarbons



Patented Nov. 7, 1933 1,933,716

UNITED STATES PATENT orrlcE MANUFACTURE OF SYNTHETIC RESINS FROMUNSATURATED HYDROCARBONS Roland B. Day. Chicago,. Ill., assignor toUniversal Oil Products Company, Chicago, 111., a corporation of SouthDakota No Drawing. Application December 18, 1931 Serial No. 581,996

6 Claims. (Cl. 260-3) This invention relates to the manufacture of tionin the absence of other polymerizable subresins and refers moreparticularly to the manustances but it has been found that morecomfacture of such resins by synthetic polymerization merciallyutilizable gums can be obtained when and condensation reactions amongorganic comsuch gum-forming reactions are permitted to 5 pounds. takeplace in the presence of aldehydes such as More particularly, theinvention has reference those mentioned above, the result being theproto a process involving the simultaneous and conduction of compositegummy substances with current polymerization of aldehydes andpetroproperties superior to those possible of formaleum fractionscontaining relatively high pertion from the two separate base materials.

30 centages of olefinic and unsaturated cyclic hy- When the distillatesavailable for use in resin drocarbons. The particular nature of thealdemanufacture contain relatively low amounts of hydes and thepetroleum fractions employed and unsaturated and polymerizableconstituents it the manner in which the composite resin may be mayfrequently be of advantage to segregate such produced will be disclosedfully in the following constituents by treating the distillates withsulis specification. furic acid, liquid sulfur dioxide, dimethylsulfateThe paint and varnish industry is familiar and other reagents capable ofreacting substanwith numerous substitutes offered for the natural tiallycompletely with or dissolving the unsatgums used in paints andvarnishes, such as gum urated constituents of the distillate. Whensulcopal, gum dammar, gum kauri, and various furic acid is employed thesludge produced may 20 grades of shellac. The properties most essentialbe hydrolyzed to liberate the combined unsatto the use of these gums istheir solubility in light urated compounds, some reappearingsubstanvolatile solvents such as turpentine, acetone and tially in thesame form in which they occurred in benzol, and their tendency to form alight-colthe distillate and some undergoing transformaored elastic filmon evaporation of the solvent. tions usually in the direction ofincreased molecu- 25 The present invention is concerned with the manlarweight and decreased unsaturation. In any so ufacture of substitutes forthese naturally-ocevent, the separated oil may be utilized directlycuring gums by polymerization of relatively cheap or may be subjected toa preliminary oxidizing materials to form condensation products havingtreatment, such as, for example, treating at a desired properties, aswill appear more fully hereslightly elevated temperature by a stream ofair so inafter. in the presence of selected metallic oxide mix- In onespecific embodiment the invention comtures. prisesthe concurrentpolymerization of aldehydes The portion of cracked distillate extractedby and oxidized petroleum distillates to form mateliquid sulfur dioxideundergoes no material rials of a resinous nature. change and may berecovered by simple evapora- Among the aldehydes which may be used maytion of the sulfur dioxide under reduced pressure be mentionedformaldehyde, d yde, para and slightly elevated temperature, accordingto dehyde, acrolein, crotonaldehyde, capronaldethe well known operationsof liquid sulfur dioxide hyde, butyraldehyde and other aldehydes oftreatments. higher molecular weight of both the aliphatic and Anothertype of material especially adapted to aromatic series of hydrocarbons,such as, for eX- use in the present invention are the polymers ample,benzaldehyde, furfural and a number of produced by passing crackedvapors over admixed aliphatic-aromatic aldehydes. sorbent materials suchas fullers earth, clays,

The petroleum fractions which it is preferred to bauxite, etc., thesematerials usually being ob- USE fO best results are the Partiallyoxidized tained in solution in the reflux from the bottom crac eddistillates p d in the t eat ent 0f of treating towerscontaining'adsorbent material, high boiling petroleum oils at elevatedtemperaand recoverable by evaporation of the excess of tures andpressures. It is well known that such unchanged 011 in which they aredissolved. In distillates contain varying proportions of unsatsome casesthese materials may be used in urated 00mp01111ds,b0th Straight Chain ylic, resin-forming condensation reactions with al- 50 and that theseclasses of compoun are pdehydes without preliminary oxidation since thetible to polymerization and condensation reacpolymerization reactionshave been already tions under the influence of oxidation, light,elecbrought out in part by the clay or other adsorbtrical energy, etc.Such distillates will form a cerent material. tain limited amount ofresinous material of in- As an example of operation for the production55 ferior quality when subjected to controlled oxidaof a soluble,fusible resin from an aldehyde and a cracked distillate, the followingcase may be cited: The sulfur dioxide extracted material from a crackedgasoline containing approximately 20 percent of unsaturates may beboiled for one hour with refluxing with an aqueous solution of 40percent formaldehyde. At the end of this heating period a two-layersystem is observed, the upper consisting mostly of an oily layer and thebottom consisting of an aqueous layer in which resinous material isemulsified and from which resin is obtained by evaporation of the water.The resin thus obtained may be light brown and transparent, soluble inacetone and alcohol and utilizable in all respects as a shellacsubstitute.

The process may be varied according to the particular type of aldehydeused, the nature of the oxidized cracked oil and the particular productsdesired in the finished resin. In a majority of cases boiling underreflux conditions may be sufiicient but in others it may be bettereconomy to use superatmospheric pressures in the digestion in order toobtain higher temperatures, increase the capacity of apparatus, andminimize losses. Catalytic materials may be used to accelerate thereactions, such as minor amounts of sulphuric acid, hydrochloric acid,sodium hydroxide, ammonia, zinc chloride, etc.

While it is generally preferable to use the more readily oxidizableconstituents of natural or synthetic petroleums, it is also within thescope of the invention to oxidize the more saturated portions, such assubstantially saturated distillates of limited boiling point range, suchoxidations tending to remove hydrogen and induce polymerizationreactions of the same general type occurring naturally in straight chainor cyclic hydrocarbons containing double bonds.

What I claim as my invention is:

1. A process for the production of synthetic resins which comprisessubjecting hydrocarbon distillates containing a substantial amount ofunsaturated hydrocarbons to the action of a solvent to separate theunsaturated hydrocarbons from the relatively saturated hydrocarbonsremoving the solvent therefrom and thereafter reacting the separatedrelatively unsaturated hydrocarbons with an aldehyde.

2. A process for the production of synthetic resins having electricalinsulating and non-corrosive properties which comprises separating therelatively unsaturated hydrocarbon components of cracked distillates bymeans of a solvent, separating the solvent therefrom and reacting thethus separated unsaturated hydrocarbons with an aldehyde.

3. A process for the production of synthetic resins which comprisessubjecting hydrocarbon distillates containing a substantial amount ofunsaturated hydrocarbons to the action of a liquid sulphur dioxide toseparate the unsaturated hydrocarbons from/the relatively saturatedhydrocarbons, removing the liquid sulphur dioxide therefrom andthereafter causing the separated relatively unsaturated hydrocarbons tobe reacted on by an aldehyde in the presence of sulphuric acid.

4. Aprocess for the production of synthetic resins having electricalinsulating and non-corrosive properties which comprises separating therelatively unsaturated hydrocarbon components of cracked distillates bymeans of a liquid sulphur dioxide, removing the liquid sulphur dioxidetherefrom and subjecting the liquid sulphur dioxide free unsaturatedhydrocarbons to reaction with an aldehyde in the presence of an alkali.

5. The process for the production of synthetic resins which comprisessubjecting cracked hydrocarbon oils to reaction with an oxidizing gas tocause the formation of oxidation products therein, subjecting theoxidized hydrocarbon mixture to the action of a solvent to separate therelatively unsaturated components therefrom separating the solvent fromthe dissolved hydr0- carbons and causing the latter to react with analdehyde.

6. The process for the production of synthetic resins which comprisessubjecting cracked hydrocarbon oils to reaction with an oxidizing gas tocause the formation of oxidation products therein, subjecting theoxidized hydrocarbon mixture to the action of a solvent to separate therelatively unsaturated components therefrom, separating the solvent fromthe dissolved hydrocarbons and causing the latter to react with analdehyde in the presence of sulphuric acid.

ROLAND B. DAY.

